Temperature-driven journey of dark excitons to efficient photocatalytic water splitting in ß-AsP.

Limited availability of photogenerated charge carriers in two-dimensional (2D) materials, due to high exciton binding energies, is a major bottleneck in achieving efficient photocatalytic water splitting (PWS). Strong excitonic effects in 2D materials demand precise attention to electron-electron correlation, electron-hole interaction and electron-phonon coupling simultaneously. In this work, we explore the temperature-dependent electronic and optical responses of an efficient photocatalyst, blue-AsP (ß-AsP), by integrating electron-phonon coupling into state-of-the-art GW + BSE calculations. Interestingly, strong electron-lattice interaction at high temperature promotes photocatalytic water splitting with an increasing supply of long-lived dark excitons. This work presents an atypical observation contrary to the general assumption that only bright excitons enhance the PWS due to prominent absorption. Dark excitons, due to the low recombination rate, exhibit long-lived photogenerated electron-hole pairs with high exciton lifetime increasing with temperature up to ∼0.25 µs.

Engineering Catalytically Active Sites by Sculpting Artificial Edges on MoS2 Basal Plane for Dinitrogen Reduction at a Low Overpotential.

Engineering catalytically active sites have been a challenge so far and often relies on optimization of synthesis routes, which can at most provide quantitative enhancement of active facets, however, cannot provide control over choosing orientation, geometry and spatial distribution of the active sites. Artificially sculpting catalytically active sites via laser-etching technique can provide a new prospect in this field and offer a new species of nanocatalyst for achieving superior selectivity and attaining maximum yield via absolute control over defining their location and geometry of every active site at a nanoscale precision. In this work, a controlled protocol of artificial surface engineering is shown by focused laser irradiation on pristine MoS2 flakes, which are confirmed as catalytic sites by electrodeposition of AuNPs. The preferential Au deposited catalytic sites are found to be electrochemically active for nitrogen adsorption and its subsequent reduction due to the S-vacancies rather than Mo-vacancy, as advocated by DFT analysis. The catalytic performance of Au-NR/MoS2 shows a high yield rate of ammonia (11.43 × 10-8  mol s-1 cm-2 ) at a potential as low as -0.1 V versus RHE and a notable Faradaic efficiency of 13.79% during the electrochemical nitrogen reduction in 0.1 m HCl.

Regulating excitonic effects in non-oxide based XPSe3 (X = Cd, Zn) monolayers towards enhanced photocatalysis for overall water splitting.

The non-oxide 2D materials have garnered considerable interest due to their potential utilization as photocatalysts, which offer a superior substitute to metal-oxide-based photocatalysts. This study investigates the impact of the dielectric environment on the size and binding energy of excitons in atomically thin, experimentally synthesized semiconducting monolayers [XPSe3, X = (Cd, Zn)] to address the critical problem of electron-hole recombination, which significantly hinders the efficiency of most photocatalysts. We employ a precise non-hydrogenic model surpassing the hydrogenic-based Mott-Wannier model. Our findings are among the first few demonstrations of an increase in exciton size (and decrease in exciton binding energy) as environmental screening increases. These findings have implications for photocatalytic water splitting and are not limited to metal phosphorus trichalcogenides, but can be applied to other classes of 2D materials as well. This work also compares metal-oxide photocatalysts, which have been the focus of much research over the past five decades, to non-oxide-based metal phosphorus trichalcogenide photocatalysts, which offer a superior alternative due to their ability to address issues such as light-harvesting inability in the visible spectrum and unwanted charge recombination centres. Furthermore, the implications of this study extend beyond photocatalysts and are significant for the design and development of next-generation optoelectronic devices that incorporate excitonic processes, such as solar cells, photodetectors, LEDs, etc.

Experimental and computational insights into luminescence in atomically precise bimetallic Au6-nCun(MPA)5 (n = 0-2) clusters.

Bimetallic nanoclusters (NCs) have emerged as a new class of luminescent materials for potential applications in sensing, bio-imaging, and light-emitting diodes (LEDs). Here, we have synthesized gold-copper bimetallic nanoclusters (AuCu NCs) using a one-step co-reduction method and tuned the emission wavelength from 520 nm to 620 nm by changing the [Cu2+]/[Au3+] molar ratio. The quantum yield (QY) increases from 6% to 13% upon incorporation of the Cu atom in the Au NCs. MALDI-TOF mass spectrometric analysis reveals that the composition of the Au NCs is Au6(MPA)5, and the bimetallic nanocluster is Au4Cu2(MPA)5, where 3-mercaptopropionic acid (MPA) is used as the capping ligand. Furthermore, we investigated the optimized structures of the as-synthesized NCs using density functional theory (DFT) along with analysis of the preferable adsorption sites using Fukui functions. We report the HOMO-LUMO gap, which is consistent with the experimentally observed red shift in the UV-Vis absorption features of the Au NCs upon copper doping. XPS studies suggest the formation of intermixing of states between the 5d orbitals of Au and the 3d orbitals of Cu in the AuCu NCs after incorporating Cu atoms into the Au NCs, which is corroborated by the DFT calculations on electronic charge transfer from the Cu to the Au atom in the NCs. The coupling between Au(I) and Cu(I) facilitates the formation of a low-lying mixed Au(I)-Cu(I) energy state. This study elaborates on the impact of Cu doping on the excited-state relaxation dynamics of AuCu NCs.

Nanocatalytic Interface to Decode the Phytovolatile Language for Latent Crop Diagnosis in Future Farms.

Crop diseases cause the release of volatiles. Here, the use of an SnO2-based chemoresistive sensor for early diagnosis has been attempted. Ionone is one of the signature volatiles released by the enzymatic and nonenzymatic cleavage of carotene at the latent stage of some biotic stresses. To our knowledge, this is the first attempt at sensing volatiles with multiple oxidation sites, i.e., ionone (4 oxidation sites), from the phytovolatile library, to derive stronger signals at minimum concentrations. Further, the sensitivity was enhanced on an interdigitated electrode by the addition of platinum as the dopant for a favorable space charge layer and for surface island formation for reactive interface sites. The mechanistic influence of oxygen vacancy formation was studied through detailed density functional theory (DFT) calculations and reactive oxygen-assisted enhanced binding through X-ray photoelectron spectroscopy (XPS) analysis.

Two-dimensional ultrathin van der Waals heterostructures of indium selenide and boron monophosphide for superfast nanoelectronics, excitonic solar cells, and digital data storage devices.

Semiconducting indium selenide (InSe) monolayers have drawn a great deal of attention among all the chalcogenide two-dimensional materials on account of their high electron mobility; however, they suffer from low hole mobility. This inherent limitation of an InSe monolayer can be overcome by stacking it on top of a boron phosphide (BP) monolayer, where the complementary properties of BP can bring additional benefits. The electronic, optical, and external perturbation-dependent electronic properties of InSe/BP hetero-bilayers have been systematically investigated within density functional theory in anticipation of its cutting-edge applications. The InSe/BP heterostructure has been found to be an indirect semiconductor with an intrinsic type-II band alignment where the conduction band minimum (CBM) and valence band maximum (VBM) are contributed by the InSe and BP monolayers, respectively. Thus, the charge carrier mobility in the heterostructure, which is mainly derived from the BP monolayer, reaches as high as 12 × 103 cm2 V-1 s-1, which is very much desired in superfast nanoelectronics. The suitable bandgap accompanied by a very low conduction band offset between the donor and acceptor along with robust charge carrier mobility, and the mechanical and dynamical stability of the heterostructure attests its high potential for applications in solar energy harvesting and nanoelectronics. The solar to electrical power conversion efficiency (20.6%) predicted in this work surpasses the efficiencies reported for InSe based heterostructures, thereby demonstrating its superiority in solar energy harvesting. Moreover, the heterostructure transits from the semiconducting state (the OFF state) to the metallic state (the ON state) by the application of a small electric field (∼0.15 V Å-1) which is brought about by the actual movement of the bands rather than via the nearly empty free electron gas (NFEG) feature. This thereby testifies to its potential for applications in digital data storage. Moreover, the heterostructure shows strong absorbance over a wide spectrum ranging from UV to the visible light of solar radiation, which will be of great utility in UV-visible light photodetectors.

Exceptional mechano-electronic properties in the HfN2 monolayer: a promising candidate in low-power flexible electronics, memory devices and photocatalysis.

The response of the electronic properties of the HfN2 monolayer to external perturbation, such as strain and electric fields, has been extensively investigated using density functional theory calculations for its device-based applications and photocatalysis. The HfN2 monolayer is found to be a semiconductor showing a direct band gap of 1.44 eV, which is widely tunable by 0.9 eV via application of biaxial strain. Furthermore, the tunability in the band edges of the HfN2 monolayer straddling the water redox potential under a biaxial strain of ±10% makes it suitable for solar energy harvesting via photocatalytic applications over a wide range (0-7) of pH. The band gap can be decreased by 29.8% under a biaxial tensile strain of 10%. Upon incorporation of spin orbit coupling (SOC) a large spin splitting at the conduction band (Δc ∼ 314 meV) and a small splitting at the valence band (Δv ∼ 32 meV) are noted, which is attributable to the orbital composition of the band edges. The spin splitting in the band edges is found to be adjustable via biaxial compressive strain. The strain dependent mechanical properties and stability reveal the ability of the HfN2 monolayer to withstand a large magnitude of strain of up to ±10%, thereby bringing about a giant tunability in its Young modulus (Y) from 66 N m-1 to 283 N m-1, which is gainfully exploitable in flexible electronics. The tunability in Y over such a wide range has not been observed in other 2D materials. Moreover, the HfN2 monolayer undergoes a transition from a semiconducting to a metallic state under the application of a normal electric field or gate voltage of 0.48 V Å-1, which may potentially serve as the OFF (semiconducting) and ON (metallic) state in devices. Interestingly, an electric field of such intensity has been realized experimentally using pulsed ac field technology. Such a small gate voltage will greatly lower its power consumption. The electronic origin of this transition from the OFF to the ON state is found to arise from unoccupied NFEG (Nearly Free Electron Gas) states. A HfN2 monolayer based tunnel field effect transistor (t-FET) is proposed herewith as a model device for low-power digital data storage, thereby paving new avenues in flexible electronics and memory devices.

Electronic and vibrational properties of stable isomers of (SiO)n((0,±)) (n = 2-7) clusters.

First-principles calculations based on density functional theory have been performed to explore the stable configurations, electronic structures, and vibrational spectra of neutral and charged silicon monoxide clusters (SiO)n((0,±)) (n = 2-7), which could be used as precursors in the synthesis of silicon nanowires. Our theoretical calculations provide new results on characteristic electron affinity, ionization potential, and vibrational spectroscopy, guiding future experiments in the synthesis of high-quality silicon nanowires. Specifically, as the number of SiO units n increases, IR spectra of (SiO)n(±) and Raman spectra of (SiO)n(-) show an evident blue shift, and Raman spectra of (SiO)n demonstrate a red shift. Moreover, most of the neutral silicon monoxide clusters have strong IR intensities and weak Raman activities, while most of the anionic counterparts have relatively weak IR intensities and strong Raman activities. Some other energetically competitive isomers of some (SiO)n((0,±)) species were also studied for comparison.

Anisotropy in colossal piezoelectricity, giant Rashba effect and ultrahigh carrier mobility in Janus structures of quintuple Bi2X3(X = S, Se) monolayers.

Due to the asymmetric structures, two-dimensional Janus materials have gained significant attention in research for their intriguing piezoelectric and spintronic properties. In the present work, quintuple Bi2X3(X = S, Se) monolayers (MLs) have been modified to create stable Janus Bi2X2Y (X ≠ Y = S, Se) MLs that display piezoelectricity in both the planes along with Rashba effect. The out-of-plane piezoelectric constant (d33) is 41.18 (-173.14) pm V-1, while the in-plane piezoelectric constant (d22) is 5.23 (6.21) pm V-1for Janus Bi2S2Se (Bi2Se2S) ML. Including spin-orbit coupling in the Janus MLs results in anisotropic giant Rashba spin splitting (RSS) at the Γ point in the valence band, with RSS proportional tod33. The Rashba constant along the Γ-K path,αRΓ- K, is 3.30 (2.27) eV Å, whereas along Γ-M,αRΓ- Mis 3.58 (3.60) eV Å for Janus Bi2S2Se (Bi2Se2S) ML. The MLs exhibit ultrahigh electron mobility (∼5442 cm2V-1s-1) and have electron to hole mobility ratio of more than 2 due to their tiny electron-effective masses. The flexibility of the MLs allows for a signification alteration in its properties, like band gap, piezoelectric coefficient, and Rashba constant, via mechanical (biaxial) strain. For the MLs, band gap andd33value are enhanced with compressive strain. The d33value of Janus Bi2Se2S reaches 4886.51 pm V-1under compressive strain. The coexistence of anisotropic colossal out-of-plane piezoelectricity, giant RSS, and ultrahigh carrier mobilities in Janus Bi2S2Se and Bi2Se2S MLs showcase their tremendous prospects in nanoelectronic, piezotronics, and spintronics devices.

Conflux of tunable Rashba effect and piezoelectricity in flexible magnesium monochalcogenide monolayers for next-generation spintronic devices.

The coupling of piezoelectric properties with Rashba spin-orbit coupling (SOC) has proven to be the limit breaker that paves the way for a self-powered spintronic device (ACS Nano, 2018, 12, 1811-1820). For further advancement in next-generation devices, a new class of buckled, hexagonal magnesium-based chalcogenide monolayers (MgX; X = S, Se, Te) have been predicted which are direct band gap semiconductors satisfying all the stability criteria. The MgTe monolayer shows a strong SOC with a Rashba constant of 0.63 eV Å that is tunable to the extent of ±0.2 eV Å via biaxial strain. Also, owing to its broken inversion symmetry and buckling geometry, MgTe has a very large in-plane as well as out-of-plane piezoelectric coefficient. These results indicate its prospects for serving as a channel semiconducting material in self-powered piezo-spintronic devices. Furthermore, a prototype for a digital logic device can be envisioned using the ac pulsed technology via a perpendicular electric field. Heat transport is significantly suppressed in these monolayers as observed from their intrinsic low lattice thermal conductivity at room temperature: MgS (9.32 W m-1 K-1), MgSe (4.93 W m-1 K-1) and MgTe (2.02 W m-1 K-1). Further studies indicate that these monolayers can be used as photocatalytic materials for the simultaneous production of hydrogen and oxygen on account of having suitable band edge alignment and high charge carrier mobility. This work provides significant theoretical insights into both the fundamental and applied properties of these new buckled MgX monolayers, which are highly suitable for futuristic applications at the nanoscale in low-power, self-powered multifunctional electronic and spintronic devices and solar energy harvesting.

Spin-Current Modulation in Hexagonal Buckled ZnTe and CdTe Monolayers for Self-Powered Flexible-Piezo-Spintronic Devices.

The next-generation spintronic device demands the gated control of spin transport across the semiconducting channel through the replacement of the external gate voltage source by the piezo potential, as experimentally demonstrated in Zhu et al. ACS Nano, 2018, 12 (2), 1811-1820. Consequently, a high level of out-of-plane piezoelectricity together with a large Rashba spin splitting is sought after in semiconducting channel materials. Inspired by this experiment, a new hexagonal buckled two-dimensional (2D) semiconductor, ZnTe, and its iso-electronic partner, CdTe, are proposed herewith. These 2D materials show a strong spin-orbit coupling (SOC), which is evidenced by a large Rashba constant of 1.06 and 1.27 eV·Å, respectively, in ZnTe and CdTe monolayers. Moreover, these Rashba semiconductors exhibit a giant out-of-plane piezoelectric coefficient (d33) = 88.68 and 172.61 pm/V, and can thereby generate a high piezo potential for gating purposes in spin field-effect transistors (spin-FETs). While the low elastic stiffness implies the mechanical flexibility or stretchability in these monolayers. The Rashba constants are found to be effectively modulated via external perturbations, such as strain and electric field. The wide band gap provides ample room for modulation in its electronic properties via external perturbations. Such scope is severely limited in previously reported narrow band gap Rashba semiconductors. The fascinating results found in this work indicate their great potential for applications in next-generation self-powered flexible-piezo-spintronic devices. Moreover, a new class of hexagonal buckled ZnX (X: S, Se, or Te) monolayers is proposed herein based on their previously synthesized bulk counterparts, while their electronic, mechanical, piezoelectric, and thermal properties have been thoroughly investigated using the state-of-art density functional theory (DFT).

Group-IV(A) Janus dichalcogenide monolayers and their interfaces straddle gigantic shear and in-plane piezoelectricity.

Inversion symmetry in the 1T-phase of pristine dichalcogenide monolayer MX2 (M = Ge, Sn; X = S, Se) is broken in their Janus structures, MXY (M = Ge, Sn; X ≠ Y = S, Se), which induces an in-plane piezoelectric coefficient, d22 = 4.09 (2.15) pm V-1 and a shear piezoelectric coefficient, d15 = 7.90 (13.68) pm V-1 in the GeSSe (SnSSe) monolayer. High flexibility arising from the small Young's modulus (60-70 N m-1) found in these Group-IV(A) Janus monolayers makes them suitable for large-scale strain engineering. Application of 7% uniaxial tensile strain increases d22 and d15 colossally to 267.07 pm V-1 and 702.34 pm V-1, respectively, thereby reaching the level of bulk piezoelectric perovskite materials. When the Janus GeSSe monolayers are stacked to form a van der Waals (vdW) homo-bilayer, d22 lies between 19.87 and 73.26 pm V-1, while d15 falls into the range between 83.01 and 604.34 pm V-1, depending on the stacking order. The chalcogen exchange energies and overall stabilities of the monolayers and bilayers confirm the feasibility of their experimental synthesis. Moreover, hole mobility in the GeSSe monolayer is greater than the electron mobility along its zigzag directions (µe = 883 cm2 V-1 s-1 and µh = 1134 cm2 V-1 s-1). Therefore, the semiconducting, flexible, and piezoelectric Janus GeSSe monolayer and bilayers are immensely promising for futuristic applications in energy harvesting, nanopiezotronic field-effect transistors, atomically thin sensors, shear/torsion actuators, transducers, self-powered circuits in nanorobotics, and electromechanical memory devices, and biomedical and other nanoelectronic applications.

Interfacial hybridization of Janus MoSSe and BX (X = P, As) monolayers for ultrathin excitonic solar cells, nanopiezotronics and low-power memory devices.

In this work, we explored the interfacial two-dimensional (2D) physics and significant advancements in the application prospects of MoSSe monolayer when it is combined with a boron pnictide (BP, BAs) monolayer in a van der Waals heterostructure (vdWH) setup. The constructed vdWHs were found to be mechanically and dynamically stable, and they form type-II p-n heterojunctions. Thus, the photogenerated electron-hole pairs are spatially separated. In the BX/MoSSe vdWHs, the BX monolayer serves as excellent donor material for MoSSe, having an ideal donor band gap of ∼1.3 eV. The small value of the conduction band offset (CBO) between the individual monolayers in the vdWHs makes it an excellent candidate for solar energy harvesting in excitonic solar cells, where the power conversion efficiencies were calculated to be 22.97% (BP/MoSSe) and 20.86% (BAs/MoSSe). Also, more than four-fold enhancement in the out-of-plane piezoelectric coefficient (d33) was observed in the MoSSe-based vdWH relative to that in the MoS2-based vdWH owing to the intrinsic built-in vertical electric field in MoSSe. This is consistent with the out-of-plane piezoelectricity brought about by the alteration in symmetry at the metal-semiconductor Schottky junction, which has been observed experimentally [M.-M. Yang, Z.-D. Luo, Z. Mi, J. Zhao, S. P. E and M. Alexe, Nature, 2020, 584, 377-381]. The results obtained in this work provide useful insights into the design of nanomaterials for future applications in nano-optoelectronics, more efficient excitonic solar cells, and nanoelectromechanical systems (NEMS). Furthermore, this work demonstrates outstanding potential for the application of these vdWHs in superfast electronics, including low-power digital data storage and memory devices, where the tunnel current between the source and drain is effectively tunable using a normal electric field of small magnitude serving as the gate voltage.

Ultra-low lattice thermal conductivity and giant phonon-electric field coupling in hafnium dichalcogenide monolayers.

Phonons in crystalline solids are of utmost importance in governing its lattice thermal conductivity (k L). In this work, k L in hafnium (Hf) dichalcogenide monolayers has been investigated based on ab initio DFT coupled to linearized Boltzmann transport equation together with single-mode relaxation-time approximation. Ultra-low k L found in HfS2 (2.19 W m-1 K-1), HfSe2 (1.23 W m-1 K-1) and HfSSe (1.78 W m-1 K-1) monolayers at 300 K, is comparable to that of the state-of-art bulk thermoelectric materials, such as, Bi2Te3 (1.6 W m-1 K-1), PbTe (2.2 W m-1 K-1) and SnSe (2.6 W m-1 K-1). Gigantic longitudinal-transverse optical (LO-TO) splitting of up to 147.7 cm-1 is noticed at the Brillouin zone-centre (Γ-point), which is much higher than that in MoS2 single layer (∼2 cm-1). It is driven by the colossal phonon-electric field coupling arising from the domination of ionic character in the interatomic bonds and Born effective or dynamical charges as high as 7.4e on the Hf ions, which is seven times that on Mo in MoS2 single layer. Enhancement in k L occurs in HfS2 (2.19 to 4.1 W m-1 K-1), HfSe2 (1.23 to 1.7 W m-1 K-1) and HfSSe (1.78 to 2.2 W m-1 K-1) upon the incorporation of the non-analytic correction term. Furthermore, the mode Grüneisen parameter is calculated to be as high as ∼2.0, at room temperature, indicating a strong anharmonicity. Moreover, the contribution of optical phonons to k L is found to be ∼12%, which is significantly high than that in single-layer MoS2. Large atomic mass of Hf (178.5 u), small phonon group velocities (4-5 km s-1), low Debye temperature (∼166 K), low bond and elastic stiffness (Young's modulus ∼75 N m-1), small phonon lifetimes (∼6 ps), low specific heat capacity (∼17 J K-1 mol-1) and strong anharmonicity are collectively found to be the factors responsible for such a low k L. These findings would be immensely helpful in designing thermoelectric interconnects at the nanoscale and 2D material-based energy harvesters.

Superhigh flexibility and out-of-plane piezoelectricity together with strong anharmonic phonon scattering induced extremely low lattice thermal conductivity in hexagonal buckled CdX (X = S, Se) monolayers.

Although CdX (X = S, Se) has been mostly studied in the field of photocatalysis, photovoltaics, their intrinsic properties, such as, mechanical, piezoelectric, electron and phonon transport properties have been completely overlooked in buckled CdX monolayers. Ultra-low lattice thermal conductivity [1.08 W m-1 K-1 (0.75 W m-1 K-1)] and high p-type Seebeck coefficient [1300 µV K-1 (850 µV K-1)] in CdS (CdSe) monolayers have been found in this work based on first-principles DFT coupled to semi-classical Boltzmann transport equations, combining both the electronic and phononic transport. The dimensionless thermoelectric figure of merit is calculated to be 0.78 (0.5) in CdS (CdSe) monolayers at room temperature, which is comparable to that of two-dimensional (2D) tellurene (0.8), arsenene and antimonene (0.8), indicating its great potential for applications in 2D thermoelectrics. Such a low lattice thermal conductivity arise from the participation of both acoustic [91.98% (89.22%)] and optical modes [8.02% (10.78%)] together with low Debye temperature [254 K (187 K)], low group velocity [4 km s-1 (3 km s-1)] in CdS (CdSe) monolayers, high anharmonicity and short phonon lifetime. Substantial cohesive energy (∼4-5 eV), dynamical and mechanical stability of the monolayers substantiate the feasibility in synthesizing the single layers in experiments. The inversion symmetry broken along the z direction causes out-of-plane piezoelectricity. |d 33| ∼ 21.6 pm V-1, calculated in CdS monolayer is found to be the highest amongst structures having atomic-layer thickness. Superlow Young's modulus ∼41 N m-1 (31 N m-1) in CdS (CdSe) monolayers, which is comparable to that of planar CdS (29 N m-1) and TcTe2 (34 N m-1), is an indicator of its superhigh flexibility. Direct semiconducting band gap, high carrier mobility (∼500 cm2 V-1 s-1) and superhigh flexibility in CdX monolayers signify its gigantic potential for applications in ultrathin, stretchable and flexible nanoelectronics. The all-round properties can be synergistically combined together in futuristic applications in nano-piezotronics as well.

Interfacing Boron Monophosphide with Molybdenum Disulfide for an Ultrahigh Performance in Thermoelectrics, Two-Dimensional Excitonic Solar Cells, and Nanopiezotronics.

A stable ultrathin 2D van der Waals (vdW) heterobilayer, based on the recently synthesized boron monophosphide (BP) and the widely studied molybdenum disulfide (MoS2), has been systematically explored for the conversion of waste heat, solar energy, and nanomechanical energy into electricity. It shows a gigantic figure of merit (ZT) > 12 (4) for p (n)-type doping at 800 K, which is the highest ever reported till date. At room temperature (300 K), ZT reaches 1.1 (0.3) for p (n)-type doping, which is comparable to experimentally measured ZT = 1.1 on the PbTe-PbSnS2 nanocomposite at 300 K, while it outweighs the Cu2Se-CuInSe2 nanocomposite (ZT = 2.6 at 850 K) and the theoretically calculated ZT = 7 at 600 K on silver halides. Lattice thermal conductivity (κl ≈ 49 W m-1 K-1) calculated at room temperature is lesser than those of black phosphorene (78 W m-1 K-1) and arsenene (61 W m-1 K-1). The nearly matched lattice constants in the commensurate lattices of the constituent monolayers help to preserve the direct band gap at the K point in the type II vdW heterobilayer of MoS2/BP, where BP and MoS2 serve as donor and acceptor materials, respectively. An ultrahigh carrier mobility of ∼20 × 103 cm2 V-1 s-1 is found, which exceeds those of previously reported transition metal dichalcogenide-based vdW heterostructures. The exciton binding energy (0.5 eV) is close to those of MoS2 (0.54 eV) and C3N4 (0.33 eV) single layers. The calculated power conversion efficiency (PCE) in the monolayer MoS2/BP heterobilayer exceeds 20%. It surpasses the efficiency in MoS2/p-Si heterojunction solar cells (5.23%) and competes with the theoretically calculated ones, as listed in the manuscript. Furthermore, a high optical absorbance (∼105 cm-1) of visible light and a small conduction band offset (0.13 eV) make MoS2/BP very promising in 2D excitonic solar cells. The out-of-plane piezoelectric strain coefficient, d33 ≈ 3.16 pm/V, is found to be enhanced 4-fold (∼14.3 pm/V) upon applying 7% vertical compressive strain on the heterobilayer, which corresponds to ∼1 kbar of hydrostatic pressure. Such a high out-of-plane piezoelectric coefficient, which can tune top-gating effects in ultrathin 2D nanopiezotronics, is a relatively new finding. As BP has been synthesized recently, experimental realization of the multifunctional, versatile MoS2/BP heterostructure would be highly feasible.

Proton-Triggered Fluorescence Switching in Self-Exfoliated Ionic Covalent Organic Nanosheets for Applications in Selective Detection of Anions.

The exfoliation of covalent organic frameworks into covalent organic nanosheets (CONs) not only helps to reduce fluorescence turn-off phenomena but also provides well-exposed active sites for fast response and recovery for various applications. The present work is an example of rational designing of a structure constructed by condensing triaminoguanidinium chloride (TGCl), an intrinsic ionic linker, with a fluorophore, 2, 5-dimethoxyterephthalaldehyde (DA), to produce highly fluorescent self-exfoliable ionic CONs (DATGCl-iCONs). These fluorescent iCONs are able to sense fluoride ions selectively down to the ppb level via the fluorescence turn-off mechanism. A closer look at the quenching mechanism via NMR, zeta potential measurement, lifetime measurement, and density functional theory calculations reveals unique proton-triggered fluorescence switching behavior of newly synthesized DATGCl-iCONs.

Experimental and Theoretical Study into Interface Structure and Band Alignment of the Cu2Zn1-x Cd x SnS4 Heterointerface for Photovoltaic Applications.

To improve the constraints of kesterite Cu2ZnSnS4 (CZTS) solar cell, such as undesirable band alignment at p-n interfaces, bandgap tuning, and fast carrier recombination, cadmium (Cd) is introduced into CZTS nanocrystals forming Cu2Zn1-x Cd x SnS4 through cost-effective solution-based method without postannealing or sulfurization treatments. A synergetic experimental-theoretical approach was employed to characterize and assess the optoelectronic properties of Cu2Zn1-x Cd x SnS4 materials. Tunable direct band gap energy ranging from 1.51 to 1.03 eV with high absorption coefficient was demonstrated for the Cu2Zn1-x Cd x SnS4 nanocrystals with changing Zn/Cd ratio. Such bandgap engineering in Cu2Zn1-x Cd x SnS4 helps in effective carrier separation at interface. Ultrafast spectroscopy reveals a longer lifetime and efficient separation of photoexcited charge carriers in Cu2CdSnS4 (CCTS) nanocrystals compared to that of CZTS. We found that there exists a type-II staggered band alignment at the CZTS (CCTS)/CdS interface, from cyclic voltammetric (CV) measurements, corroborated by first-principles density functional theory (DFT) calculations, predicting smaller conduction band offset (CBO) at the CCTS/CdS interface as compared to the CZTS/CdS interface. These results point toward efficient separation of photoexcited carriers across the p-n junction in the ultrafast time scale and highlight a route to improve device performances.

Superhigh out-of-plane piezoelectricity, low thermal conductivity and photocatalytic abilities in ultrathin 2D van der Waals heterostructures of boron monophosphide and gallium nitride.

A stable 2D van der Waals (vdW) heterobilayer, constituted by boron monophosphide (BP) and Gallium Nitride (GaN) monolayers, has been explored for different kinds of energy conversion and nanoelectronics. The nearly matched lattice constants of GaN and BP are commensurate with each other in their lattice structures. The out-of-plane inversion asymmetry coupled with the large difference in atomic charges between the GaN and BP monolayers induces in the heterobilayer a giant out-of-plane piezoelectric coefficient (|d33|max ≈ 40 pm V-1), which is the highest ever reported in 2D materials of a finite thickness. It is much higher than the out-of-plane piezoelectric coefficient reported earlier in multilayered Janus transition metal dichalcogenide MXY (M = Mo, W; X, Y = S, Se, Te) (|d33|max = 10.57 pm V-1). Such a high out-of-plane piezoelectricity found in a BP/GaN heterobilayer can bring about gigantic strain-tunable top gating effects in nanopiezotronic devices based on the same. Moreover, electron mobility (∼104 cm2 V-1 s-1) is much higher than that of transition metal dichalcogenides and conventional semiconductors. The origin of low lattice thermal conductivity (κL ∼ 25.25 W m-1 K-1) in BP/GaN at room temperature, which is lower than that of black phosphorene (78 W m-1 K-1), buckled arsenene (61 W m-1 K-1), BCN (90 W m-1 K-1), MoS2 (34.5 W m-1 K-1) and WS2 (32 W m-1 K-1) monolayers, has been systematically investigated via phonon dispersion, lattice thermal conductivity, phonon lifetime and mode Grüneisen parameters. The valence band maximum (VBM) and conduction band minimum (CBM) arising from GaN and BP monolayers respectively result in a type II vdW heterobilayer, which is found to be thermodynamically favorable for photocatalytic water splitting in both acidic and neutral media. The exciton binding energies are comparable to those of MoS2 and C3N4 single layers, while the absorbance reaches as high as ∼105 cm-1 in the visible wavelength region. The emergence of high piezoelectricity, high carrier mobility, low lattice thermal conductivity and photocatalytic water splitting abilities in the proposed vdW heterobilayer signifies enormous potential for its versatile applications in nanoscale energy harvesting, e.g., nano-sensors in medical devices, future nanopiezotronics, 2D thermoelectrics and solar energy conversion.

Compressive strain induced enhancement in thermoelectric-power-factor in monolayer MoS2 nanosheet.

Strain and temperature induced tunability in the thermoelectric properties in monolayer MoS2 (ML-MoS2) has been demonstrated using density functional theory coupled to semi-classical Boltzmann transport theory. Compressive strain, in general and uniaxial compressive strain (along the zig-zag direction), in particular, is found to be most effective in enhancing the thermoelectric power factor, owing to the higher electronic mobility and its sensitivity to lattice compression along this direction. Variation in the Seebeck coefficient and electronic band gap with strain is found to follow the Goldsmid-Sharp relation. n-type doping is found to raise the relaxation time-scaled thermoelectric power factor higher than p-type doping and this divide widens with increasing temperature. The relaxation time-scaled thermoelectric power factor in optimally n-doped ML-MoS2 is found to undergo maximal enhancement under the application of 3% uniaxial compressive strain along the zig-zag direction, when both the (direct) electronic band gap and the Seebeck coefficient reach their maximum, while the electron mobility drops down drastically from 73.08 to 44.15 cm2 V-1 s-1. Such strain sensitive thermoelectric responses in ML-MoS2 could open doorways for a variety of applications in emerging areas in 2D-thermoelectrics, such as on-chip thermoelectric power generation and waste thermal energy harvesting.